Dioxepane substituted amides

ABSTRACT

This invention discloses new compounds of the formula   &lt;IMAGE&gt; WHEREIN R1 is selected from the group consisting of hydrogen and alkyl; X is halogen; R2 is selected from the group consisting of alkyl, alkenyl and alkynyl; n is the integer 1 or 2; Z is alkyl; and m is an integer from 0 to 4. Further disclosed are herbicidal compositions utilizing the aforedescribed compounds.

This invention relates to new compositions of matter and morespecifically relates to new chemical compounds of the formula ##STR2##wherein R¹ is selected from the group consisting of hydrogen and alkyl;X is halogen; R² is selected from the group consisting of alkyl, alkenyland alkynyl; n is the integer 1 or 2; Z is alkyl; and m is an integerfrom 0 to 4.

The compounds of the present invention are useful as herbicides and areexceptionally suitable as preemergence grass herbicides. Morover thesubject compounds are useful for stunting the growth of ornamental turfreducing the need for mowing.

In a preferred embodiment of the present invention R¹ is selected fromthe group consisting of hydrogen and lower alkyl; X is selected from thegroup consisting of chlorine and bromine; R² is selected from the groupconsisting of alkyl of up to ten carbon atoms, lower alkenyl and loweralkynyl; n is the integer 1 or 2; Z is lower alkyl and m is an integerfrom 0 to 2.

The term lower as used herein designates a straight or branched carbonchain of up to six carbon atoms.

The compounds of the present invention can be prepared by reacting acompound of the formula ##STR3## wherein R², n, Z and m are asheretofore described, with an α-haloalkanoyl chloride of the formula##STR4## wherein R¹ and X are as heretofore described. This reaction canbe effected by combining a compound of formula II with an aboutequimolar or slight excess molar amount of a compound of formula III inan inert organic reaction medium, such as benzene, in the presence of anacid acceptor, such as an alkali metal carbonate or bicarbonate or atertiary amine, at a temperature of about -10° C to about 25° C andstirring the resulting mixture for a period of from about 15 to about120 minutes. After this time the reaction mixture can be washed withwater to remove inorganic salts and stripped of solvent to yield thedesired product. This product can then be used as such or can be furtherpurified by conventional means.

The compounds of formula II can be prepared by reacting a substitutedamine of the formula ##STR5## wherein R² is as heretofore described witha compound of the formula ##STR6## wherein Y is chlorine or bromine andn, Z and m are as heretofore described. This reaction can be effected bycombining the compound of formula V with an excess molar amount of theamine of formula IV and heating the mixture with agitation for a periodof from 1/2 to 8 hours. When a very low boiling amine is used apressurized vessel can be preferably utilized. After this time stronginorganic base such as aqueous sodium hydroxide is added to the reactionmixture to liberate the free amine from its hydrochloride. The organicphase is then separated from the aqueous phase, dried over anhydrousmagnesium sulfate and distilled to yield the desired product.

The compounds of formula V when not available can be prepared byreacting an acetal of the formula ##STR7## wherein Y and n are asheretofore described and R³ and R⁴ are methyl or ethyl, with a diol ofthe formula ##STR8## wherein each R is hydrogen or alkyl, provided amaximum of four R groups are alkyl. This reaction can be effected bycombining the compound of formula VI with the compound of formula VII inabout equimolar amounts and in the presence of an acid catalyst such assulfuric acid or toluene sulfonic acid under anhydrous conditions. Themixture can be heated for a period of from about 1 to about 4 hours andthe alcohol removed as it is formed. After this time the reactionmixture can be distilled under reduced pressure to yield the desiredproduct.

The compounds of the present invention can also be prepared by reactingan acetal of the formula ##STR9## wherein R¹, X, R², n, R³ and R⁴ are asheretofore described with an about equimolar amount of the diol offormula VII. This reaction can be effected by combining the reactants inthe presence of a catalytic amount of toluene sulfonic acid underanhydrous conditions. The reaction mixture can be heated and the alcoholremoved by distillation as it is formed. After no more alcohol is givenoff sodium carbonate can be added and the reaction mixture distilled toyield the desired product.

The compounds of formula VIII can be prepared by reacting a compound ofthe formula ##STR10## wherein R², n, R³ and R⁴ are as heretoforedescribed, with a compound of formula III. This reaction can be effectedin the same manner as the reaction between compound II and III describedabove.

The compounds of formula IX can be prepared by reacting the amine offormula IV with an about equimolar amount of the acetal of formula VI.This reaction can be effected by combining the reactants in an inertorganic reaction medium in the presence of an acid acceptor. Thereaction mixture can be heated at reflux for a period of from 2 to 24hours. After this time the mixture is filtered and stripped of solventto yield the desired product.

Exemplary suitable diols of formula VII for preparing the compounds ofthe present invention are butandiol-1,4, pentandiol-1,4, hexandiol-1,4,heptandiol-1,4, octandiol-1,4, hexandiol-2,5, octandiol-2,5,2-methylbutandiol-1,4, 2,5-dimethylhexanediol-2,5,3,4-dimethylhexandiol-2,5, 2,3,4,5-tetramethylhexandiol-2,5 and thelike.

Exemplary suitable amines of formula IV are methylamine, ethylamine,propylamine, butylamine, pentylamine, hexylamine, allylamine,2-butenylamine, 2-pentenylamine, 3-pentenylamine, 4-hexenylamine,5-hexenylamine, proparygylamine, 2-butynylamine, 3-butynylamine,1,1-dimethylpropargylamine, 1,1-diethylpropargylamine, 4-hexynylamine,isopropylamine, t-butylamine and the like.

Exemplary suitable α-haloalkanoyl chlorides of formula III for preparingthe compounds of this invention are chloroacetyl chloride,α-chloropropanoyl chloride, α-bromobutanoyl chloride, α-chloropentanoylchloride, α-chlorohexanoyl chloride, α-chloro-α-methylbutanoyl chloride,α-chloroheptanoyl chloride and the like.

EXAMPLE 1 Preparation of the Diethylacetal of2-Isopropylaminoacetaldehyde

The diethylacetal of 2-bromoacetaldehyde (118 grams) and isopropylamine(260 ml) were charged into a Parr Shaker. The shaker was sealed andheated with an infra-red lamp with agitation to a pressure of about 50p.s.i. Heating was then stopped and the mixture was shaken for anadditional 30 minutes. After this time aqueous sodium hydroxide (90 ml;50% concentration) was added to the reaction mixture with stirring. Theorganic phase was separated from the aqueous phase, was dried anddistilled under reduced pressure to yield the desired product thediethylacetal of 2-isopropylaminoacetaldehyde as the residue.

EXAMPLE 2 Preparation ofN-Isopropyl-N-(2,2-diethoxyethyl)-α-chloroacetamide

The diethylacetal of 2-isopropylaminoacetaldehyde (68 grams), benzene(100 ml), water (100 ml) and sodium carbonate (44 grams) were chargedinto a glass reaction vessel equipped with a mechanical stirrer andthermometer. The reaction mixture was cooled to a temperature of 5° C to10° C and chloroacetyl chloride (30 ml) was added dropwise withstirring. Stirring was continued until the reaction mixture reached roomtemperature. After this time the organic phase was separated from theaqueous phase, was washed with water and dried over anhydrous magnesiumsulfate. The dried solution was filtered and the filtrate stripped ofsolvent to yield the desired productN-isopropyl-N-(2,2-diethoxyethyl)-α-chloroacetamide as the residue.

EXAMPLE 3 Preparation ofN-Isopropyl-N-(1,3-dioxepan-2-ylmethyl)-α-chloroacetamide

N-Isopropyl-N-(2,2-diethoxyethyl)-α-chloroacetamide (10 grams),butandiol-1,4 (3.52 ml) and trace amounts of toluenesulfonic acid werecharged into a glass reaction vessel equipped with a mechanical stirrer,thermometer and reflux condenser. The reaction mixture was heated untilno more ethanol was given off. After this time sodium carbonate (1 gram)was added to the mixture with stirring and the resulting mixture wasdistilled to yield the desired productN-isopropyl-N-(1,3-dioxepan-2-ylmethyl)-α-chloroacetamide as an oil.

EXAMPLE 4 Preparation ofN-Isopropyl-N-(5,6-dimethyl-1,3-dioxepan-2-ylmethyl)-α-chloroacetamide

N-Isopropyl-N-(2,2-diethoxyethyl)-α-chloroacetamide (10 grams),2,3-dimethylbutandiol-1,4 (4.5 grams) and trace amounts oftoluenesulfonic acid are charged into a glass reaction vessel equippedwith a mechanical stirrer, thermometer and reflux condenser. Thereaction mixture is heated until no more ethanol is given off. Afterthis time sodium carbonate (1 gram) is added to the mixture withstirring and the resulting mixture is distilled to yield the desiredproductN-isopropyl-N-(5,6-dimethyl-1,3-dioxepan-2-ylmethyl)-α-chloroacetamideas an oil.

EXAMPLE 5 Preparation of the Diethylacetal of 2-Allylaminoacetaldehyde

The diethylacetal of 2-bromoacetaldehyde (118 grams) and allylamine (250ml) are charged into a Parr Shaker. The shaker is sealed and heated withan infra-red lamp, with agitation, to a pressure of about 50 p.s.i.Heating is then stopped and the mixture is shaken for an additional 30minutes. After this time aqueous sodium hydroxide (90 ml; 50%concentration) is added to the reaction mixture with stirring. Theorganic phase is then separated from the aqueous phase, is dried and isdistilled under reduced pressure to yield the desired product thediethylacetal of 2-allylaminoacetaldehyde.

EXAMPLE 6 Preparation of N-Allyl-N-(2,2-diethoxyethyl)-α-chloroacetamide

The diethylacetal of 2-allylaminoacetaldehyde (50 grams), benzene (100ml), water (100 ml) and sodium carbonate (40 grams) are charged into aglass reaction vessel equipped with a mechanical stirrer andthermometer. The reaction mixture is cooled to a temperature of 5° C to10° C and chloroacetyl chloride (30 ml) is added dropwise with stirring.Stirring is continued until the reaction mixture reaches roomtemperature. After this time the organic phase is separated from theaqueous phase, is washed with water and dried over anhydrous magnesiumsulfate. The dried solution is filtered and stripped of solvent to yieldthe desired product N-allyl-N-(2,2-diethoxyethyl)-α-chloroacetamide.

EXAMPLE 7 Preparation ofN-Allyl-N-(1,3-dioxepan-2-ylmethyl)-α-chloroacetamide

N-Allyl-N-(2,2-diethoxyethyl)-α-chloroacetamide (10 grams),butandiol-1,4 (3 ml) and trace amounts of toluenesulfonic acid arecharged into a glass reaction vessel equipped with a mechanical stirrer,thermometer and reflux condenser. The reaction mixture is heated untilno more ethanol is given off. After this time sodium carbonate (1 gram)is added to the mixture with stirring and the resulting mixture isdistilled to yield the desired productN-allyl-N-(1,3-dioxepan-2-ylmethyl)-α-chloroacetamide.

EXAMPLE 8 Preparation of the Diethylacetal of2-Propargylaminoacetaldehyde

The diethylacetal of 2-bromoacetaldehyde (118 grams) and propargylamine(250 ml) are charged into a Parr Shaker. The shaker is sealed and heatedwith an infra-red lamp, with agitation, to a pressure of about 50 p.s.i.Heating is then stopped and the mixture is shaken for an additional 30minutes. After this time aqueous sodium hydroxide (90 ml; 50%concentration) is added to the reaction mixture with stirring. Theorganic phase is then separated from the aqueous phase, is dried and isdistilled under reduced pressure to yield the desired product thediethylacetal of 2-propargylaminoacetaldehyde.

EXAMPLE 9 Preparation ofN-Propargyl-N-(2,2-diethoxyethyl)-α-chloroacetamide

The diethylacetal of 2-propargylaminoacetaldehyde (50 grams), benzene(100 ml), water (100 ml) and sodium carbonate (40 grams) are chargedinto a glass reaction vessel equipped with a mechanical stirrer andthermometer. The reaction mixture is cooled to a temperature of 5° C to10° C and chloroacetyl chloride (30 ml) is added dropwise with stirring.Stirring is continued until the reaction mixture reaches roomtemperature. After this time the organic phase is separated from theaqueous phase, is washed with water and dried over anhydrous magnesiumsulfate. The dried solution is filtered and stripped of solvent to yieldthe desired product N-propargyl-N-(2,2-diethoxyethyl)-α-chloroacetamide.

EXAMPLE 10 Preparation ofN-Propargyl-N-(1,3-dioxepan-2-ylmethyl)-α-chloroacetamide

N-Propargyl-N-(2,2-diethoxyethyl)-α-chloroacetamide (10 grams),butandiol-1,4 (3 ml) and trace amounts of toluenesulfonic acid arecharged into a glass reaction vessel equipped with a mechanical stirrer,thermometer and reflux condenser. The reaction mixture is heated untilno more ethanol is given off. After this time sodium carbonate (1 gram)is added to the mixture with stirring and the resulting mixture isdistilled to yield the desired productN-propargyl-N-(1,3-dioxepan-2-ylmethyl)-α-chloroacetamide.

EXAMPLE 11 Preparation of the Diethylacetal of 2-Methylaminoacetaldehyde

The diethylacetal of 2-bromoacetaldehyde (118 grams) and methylamine(250 ml) are charged into a Parr Shaker. The shaker is sealed and heatedwith an infra-red lamp, with agitation, to a pressure of about 50 p.s.i.Heating is then stopped and the mixture is shaken for an additional 30minutes. After this time aqueous sodium hydroxide (90 ml; 50%concentration) is added to the reaction mixture with stirring. Theorganic phase is then separated from the aqueous phase, is dried and isdistilled under reduced pressure to yield the desired product thediethylacetal of 2-methylaminoacetaldehyde.

EXAMPLE 12 Preparation ofN-Methyl-N-(2,2-diethoxyethyl)-α-bromoacetamide

The diethylacetal of 2-methylaminoacetaldehyde (50 grams), benzene (100ml), water (100 ml) and sodium carbonate (40 grams) are charged into aglass reaction vessel equipped with a mechanical stirrer andthermometer. The reaction mixture is cooled to a temperature of 5° C to10° C and bromoacetyl chloride (30 ml) is added dropwise with stirring.Stirring is continued until the reaction mixture reaches roomtemperature. After this time the organic phase is separated from theaqueous phase, is washed with water and dried over anhydrous magnesiumsulfate. The dried solution is filtered and stripped of solvent to yieldthe desired product N-methyl-N-(2,2-diethoxyethyl)-α-bromoacetamide.

EXAMPLE 13 Preparation ofN-Methyl-N-(1,3-dioxepan-2-ylmethyl)-α-bromoacetamide

N-Methyl-N-(2,2-diethoxyethyl)-α-bromoacetamide (10 grams),butandiol-1,4 (3 ml) and trace amounts of toluenesulfonic acid arecharged into a glass reaction vessel equipped with a mechanical stirrer,thermometer and reflux condenser. The reaction mixture is heated untilno more ethanol is given off. After this time sodium carbonate (1 gram)is added to the mixture with stirring and the resulting mixture isdistilled to yield the desired productN-methyl-N-(1,3-dioxepan-2-yl-methyl)-α-bromoacetamide.

EXAMPLE 14 Preparation of the Diethylacetal of 2-Ethylaminoacetaldehyde

The diethylacetal of 2-bromoacetaldehyde (118 grams) and ethylamine (250ml) are charged into a Parr Shaker. The shaker is sealed and heated withan infra-red lamp, with agitation, to a pressure of about 50 p.s.i.Heating is then stopped and the mixture is shaken for an additional 30minutes. After this time aqueous sodium hydroxide (90 ml; 50%concentration) is added to the reaction mixture with stirring. Theorganic phase is then separated from the aqueous phase, is dried and isdistilled under reduced pressure to yield the desired product thediethylacetal of 2-ethylaminoacetaldehyde.

EXAMPLE 15 Preparation ofN-Ethyl-N-(2,2-diethoxyethyl)-α-bromoproprionamide

The diethylacetal of 2-ethylaminoacetaldehyde (50 grams), benzene (100ml), water (100 ml) and sodium carbonate (40 grams) are charged into aglass reaction vessel equipped with a mechanical stirrer andthermometer. The reaction mixture is cooled to a temperature of 5° C to10° C and α-bromopropionyl chloride (30 ml) is added dropwise withstirring. Stirring is continued until the reaction mixture reaches roomtemperature. After this time the organic phase is separated from theaqueous phase, is washed with water and dried over anhydrous magnesiumsulfate. The dried solution is filtered and stripped of solvent to yieldthe desired product N-ethyl-N-(2,2-diethoxyethyl)-α-bromopropionamide.

EXAMPLE 16 Preparation ofN-Ethyl-N-(1,3-dioxepan-2-ylmethyl)-α-bromoproprionamide

N-Ethyl-N-(2,2-diethoxyethyl)-α-bromoproprionamide (10 grams),butandiol-1,4 (3 ml) and trace amounts of toluenesulfonic acid arecharged into a glass reaction vessel equipped with a mechanical stirrer,thermometer and reflux condenser. The reaction mixture is heated untilno more ethanol is given off. After this time sodium carbonate (1 gram)is added to the mixture with stirring and the resulting mixture isdistilled to yield the desired productN-ethyl-N-(1,3-dioxepan-2-ylmethyl)-α-bromoproprionamide.

Additional compounds with the scope of the present invention which canbe prepared by the procedures of the foregoing examples are furtherexemplified by the following:

N-methyl-N-(4-methyl-1,3-dioxepan-2-ylmethyl)-α-chloroacetamide,N-ethyl-N-(4-ethyl-1,3-dioxepan-2-ylmethyl)-α-chloroacetamide,N-propyl-N-(5-propyl-1,3-dioxepan-2-ylmethyl)-α-chloroacetamide,N-butyl-N-(5-butyl-1,3-dioxepan-2-ylmethyl)-α-chloroacetamide,N-pentyl-N-(5-pentyl-1,3-dioxepan-2-ylmethyl)-α-chloroacetamide,N-hexyl-N-(5-1,3-dioxepan-2-ylmethyl)-α-chloroacetamide,N-allyl-N-(4,5-dimethyl-1,3-dioxepan-2-ylmethyl)-α-chloroacetamide,N-but-3-enyl-N-(4,5,6-trimethyl-1,3-dioxepan-2-ylmethyl)-α-chloroacetamide,N-pent-4-enyl-N-(5-ethyl-1,3-dioxepan-2-ylethyl)-α-bromobutanamide,N-hex-4-enyl-N-(5-ethyl-1,3-dioxepan-2-ylethyl)-α-chlorobutanamide,N-but-3-ynyl-N-(5-ethyl-1,3-dioxepan-2-ylethyl)-α-iodopentanamide,N-pent-3-ynyl-N-(1,3-dioxepan-2-ylethyl)-α-chlorohexanamide,N-hex-4-ynyl-N-(1,3-dioxepan-2-ylethyl)-α-chloroheptanamide.

For practical use as herbicides the compounds of this invention aregenerally incorporated into herbicidal compositions which comprise aninert carrier and a herbicidally toxic amount of such a compound. Suchherbicidal compositions, which can also be called formulations, enablethe active compound to be applied conveniently to the site of the weedinfestation in any desired quantity. These compositions can be solidssuch as dusts, granules, or wettable powders; or they can be liquidssuch as solutions, aerosols, or emulsifiable concentrates.

For example, dusts can be prepared by grinding and blending the activecompound with a solid inert carrier such as the talcs, clays, silicas,pyrophyllite, and the like. Granular formulations can be prepared byimpregnating the compound, usually dissolved in a suitable solvent, ontoand into granulated carriers such as the attapulgites or thevermiculites, usually of a particle size range of from about 0.3 to 1.5mm. Wettable powders, which can be dispersed in water or oil to anydesired concentration of the active compound, can be prepared byincorporating wetting agents into concentrated dust compositions.

In some cases the active compounds are sufficiently soluble in commonorganic solvents such as kerosene or xylene so that they can be useddirectly as solutions in these solvents. Frequently, solutions ofherbicides can be dispersed under super-atmospheric pressure asaerosols. However, preferred liquid herbicidal compositions areemulsifiable concentrates, which comprise an active compound accordingto this invention and as the inert carrier, a solvent and an emulsifier.Such emulsifiable concentrates can be extended with water and/or oil toany desired concentration of active compound for application as spraysto the site of the weed infestation. The emulsifiers most commonly usedin these concentrates are nonionic or mixtures of nonionic with anionicsurface-active agents. With the use of some emulsifier systems aninverted emulsion (water in oil) can be prepared for direct applicationto weed infestations.

A typical herbicidal composition according to this invention isillustrated by the following example, in which the quantities are inparts by weight.

EXAMPLE 17 Preparation of a Dust

Product of Example 3--10

Powdered Talc--90

The above ingredients are mixed in a mechanical grinder-blender and areground until a homogeneous, free-flowing dust of the desired particlesize is obtained. This dust is suitable for direct application to thesite of the weed infestation.

The compounds of this invention can be applied as herbicides in anymanner recognized by the art. One method for the control of weedscomprises contacting the locus of said weeds with a herbicidalcomposition comprising an inert carrier and as an essential activeingredient, in a quantity which is herbicidally toxic to said weeds, acompound of the present invention. The concentration of the newcompounds of this invention in the herbicidal compositions will varygreatly with the type of formulation and the purpose for which it isdesigned, but generally the herbicidal compositions will comprise fromabout 0.05 to about 95 percent by weight of the active compounds of thisinvention. In a preferred embodiment of this invention, the herbicidalcompositions will comprise from about 5 to about 75 percent by weight ofthe active compound. The compositions can also comprise such additionalsubstances as other pesticides, such as insecticides, nematocides,fungicides, and the like; stabilizers, spreaders, deactivators,adhesives, stickers, fertilizers, activators, synergists, and the like.

The compounds of the present invention are also useful when combinedwith other herbicides and/or defoliants, dessicants, growth inhibitors,and the like in the herbicidal compositions heretofore described. Theseother materials can comprise from about 5% to about 95% of the activeingredients in the herbicidal compositions. Use of combinations of theseother herbicides and/or defoliants, dessicants, etc. with the compoundsof the present invention provide herbicidal compositions which are moreeffective in controlling weeds and often provide results unattainablewith separate compositions of the individual herbicides. The otherherbicides, defoliants, dessicants and plant growth inhibitors, withwhich the compounds of this invention can be used in the herbicidalcompositions to control weeds, can include chlorophenoxy herbicides suchas 2,4-D, 2,4,5-T, MCPA, MCPB, 4(2,4-DB), 2,4-DEB, 4-CPB, 4-CPA, 4-CPP,2,4,5-TB, 2,4,5-TES, 3,4-DA, silvex and the like; carbamate herbicidessuch as IPC, CIPC, swep, barban, BCPC, CEPC, CPPC, and the like;thiocarbamate and dithiocarbamate herbicides such as CDEC, methamsodium, EPTC, diallate, PEBC, perbulate, vernolate and the like;substituted urea herbicides such as norea, siduron, dichloral urea,chloroxuron, cycluron, fenuron, monuron, monuron TCA, diuron, linuron,monolinuron, neburon, buturon, trimeturon and the like; symmetricaltriazine herbicides such as simazine, chlorazine, atraone, desmetryne,norazine, ipazine, prometryn, atrazine, trietazine, simetone, prometone,propazine, ametryne and the like; chloroacetamide herbicides such asalpha-chloro-N,N-dimethylacetamide, CDEA, CDAA,alpha-chloro-N-isopropylacetamide, 2-chloro-N-isopropylacetanilide,4-(chloroacetyl)morpholine, 1-(chloroacetyl)-piperidine and the like;chlorinated aliphatic acid herbicides such as TCA, dalapon,2,3-dichloropropionic acid, 2,2,3-TPA and the like; chlorinated benzoicacid and phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6-TBA,dicamba, tricamba, amiben, fenac, PBA,2-methoxy-3,6-dichlorophenylacetic acid,3-methoxy-2,6-dichlorophenylacetic acid,2-methoxy-3,5,6-trichlorophenylacetic acid, 2,4-dichloro-3-nitrobenzoicacid and the like; and such compounds as aminotriazole, maleichydrazide, phenyl mercuric acetate, endothal, biuret, technicalchlordane, dimethyl 2,3,5,6-tetrachloroterephthalate, diquat, erbon,DNC, DNBP, dichlobenil, DPA, diphenamid, dipropalin, trifluralin, solan,dicryl, merphos, DMPA, DSMA, MSMA, potassium azide, acrolein, benefin,bensulide, AMS, bromacil, 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione,bromoxynil, cacodylic acid, CMA, CPMF, cypromid, DCB, DCPA, dichlone,diphenatril, DMTT, DNAP, EBEP, EXD, HCA, ioxynil, IPX, isocil, potassiumcyanate, MAA, MAMA, MCPES, MCPP, MH, molinate, NPA, OCH, paraquat, PCP,picloram, DPA, PCA, pyrichlor, sesone, terbacil, terbutol, TCBA,brominil, CP-50144, H-176-1, H-732, M-2901, planavin, sodiumtetraborate, calcium cyanamid, DEF, ethyl xanthogen disulfide, sindone,sindone B, propanil and the like. Such herbicides can also be used inthe methods and compositions of this invention in the form of theirsalts, esters, amides, and other derivatives whenever applicable to theparticular parent compounds.

Weeds are undesirable plants growing where they are not wanted, havingno economic value, and interfering with the production of cultivatedcrops, with the growing of ornamental plants, or with the welfare oflivestock. Many types of weeds are known, including annuals such aspigweed, lambsquarters, foxtail, crabgrass, wild mustard, fieldpennycress, ryegrass, goose grass, chickweed, wild oats, velvet-leaf,purslane, barnyardgrass, smartweed, knotweed, cocklebur, wild buckwheat,kochia, medic, corn cockle, ragweed, sow-thistle, coffeeweed, croton,cuphea, dodder, fumitory, groundsel, hemp nettle, knawel, spurge,spurry, emex, jungle rice, pondweed, dog fennel, carpetweed,morningglory, bedstraw, ducksalad, naiad, cheatgrass, fall panicum,jimsonweed, witchgrass, switchgrass, watergrass, teaweed, wild turnipand sprangletop; biennials such as wild carrot, matricaria, wild barley,campion, chamomile, burdock, mullein, round-leaved mallow, bull thistle,hounds-tongue, moth mullein and purple star thistle; or perennials suchas white cockle, perennial ryegrass, Johnsongrass, Canada thistle, hedgebindweed, Bermuda grass, sheep sorrel, curly dock, nutgrass, fieldchickweed, dandelion, campanula, field bindweed, Russian knapweed,mesquite, toadflax, yarrow, aster, gromwell, horsetail, ironweed,sesbania, bulrush, cattail, winter-cress, horsenettle, nutsedge,milkweed and sicklepod.

Similarly, such weeds can be classified as broadleaf or grassy weeds. Itis economically desirable to control the growth of such weeds withoutdamaging beneficial plants or livestock.

The new compounds of this invention are particularly valuable for weedcontrol because they are toxic to many species and groups of weeds. Theexact amount of compound required will depend on a variety of factors,including the hardiness of the particular weed species, weather, type ofsoil, method of application, the kind of beneficial plants in the samearea and the like. Thus, while the application of up to only about oneor two ounces of active compound per acre may be sufficient for goodcontrol of a light infestation of weeds growing under adverseconditions, the application of ten pounds or more of an active compoundper acre may be required for good control of a dense infestation ofhardy perennial weeds growing under favorable conditions.

The herbicidal toxicity of the new compounds of this invention can beillustrated by many of the established testing techniques known to theart, such as pre- and post-emergence testing.

The herbicidal activity of the compounds of this invention wasdemonstrated by experiments carried out for the pre-emergence control ofa variety of weeds. In these experiments small plastic greenhouse potsfilled with dry soil were seeded with the various weed seeds.Twenty-four hours or less after seeding the pots were sprayed with wateruntil the soil was wet and the test compounds formulated as aqueousemulsions of acetone solutions containing emulsifiers were sprayed atthe indicated concentrations on the surface of the soil.

After spraying, the soil containers were placed in the greenhouse andprovided with supplementary heat as required and daily or more frequentwatering. The plants were maintained under these conditions for a periodof 21 days, at which time the condition of the plants and the degree ofinjury to the plants was rated on a scale of from 0 to 10, as follows: 0= no injury, 1,2 = slight injury, 3,4 = moderate injury, 5,6 =moderately severe injury, 7,8,9 = severe injury and 10 = death. Theeffectiveness of these compounds is demonstrated by the data in Table I.

The herbicidal activity of the compounds of this invention was alsodemonstrated by experiments carried out for the post-emergence controlof a variety of weeds. In these experiments the compounds to be testedwere formulated as aqueous emulsions and sprayed at the indicated dosageon the foliage of the weeds that have attained a prescribed size. Afterspraying, the plants were placed in a greenhouse and watered daily ormore frequently. Water was not applied to the foliage of the treatedplants. The severity of the injury was determined 14 days aftertreatment and was rated on the scale of from 0 to 10 heretoforedescribed. The effectiveness of these compounds is demonstrated by thedata in Table II.

                                      TABLE I                                     __________________________________________________________________________    Weed Species                                                                  TestRate                                                                      Com-lbs/                                                                      poundacre                                                                           YNSG                                                                              WOAT JMWD VTLF                                                                              JNGS                                                                              PIGW                                                                              WMSTD                                                                              YLFX                                                                              BNGS                                                                              CBGS                                                                              CTGS                                                                              MNGY BDWD                __________________________________________________________________________    Product8                                                                            9   3    4    4   9   6   0    9   9   7   3   3    --                  of2   9   2    2    0   4   0   0    6   9   5   1   0    --                  Ex. 31                                                                              0   0    0    0   6   0   0    6   9   3   0   3    --                  __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________    Weed Species                                                                  Test Rate                                                                     Comp.lbs/                                                                     poundacre                                                                           YNSG                                                                              WOAT JMWD VTLF                                                                              JNGS                                                                              GIGW                                                                              WMSTD                                                                              YLFX                                                                              BNGS                                                                              CBGS                                                                              CYHGS                                                                             MNGY BDWD                __________________________________________________________________________    Product8                                                                            4   3    2    --  6   4   3    8   6   4   --  7    1                   of2   3   2    0    --  1   3   0    5   6   0   --  2    0                   Ex. 31                                                                              3   0    0    --  0   1   0    5   6   0   --  2    0                   __________________________________________________________________________     YNSG = Yellow Nutsedge                                                        WOAT = Wild OatsJMWD = JimsonweedVTLF =                                       JNGS = Johnsongrass                                                           PIGW = Pigweed                                                                WMSTD = Wild Mustard                                                          YLFX = Yellow Foxtail                                                         BNGS = Barnyardgrass                                                          CBGS = Crabgrass                                                              CTGS = Cheatgrass                                                             MNGY = Wild Morningglory                                                      BDWD = Bindweed                                                          

We claim:
 1. A compound of the formula ##STR11## wherein R¹ is selectedfrom the group consisting of hydrogen and lower alkyl; X is chlorine orbromine; R² is, lower alkenyl; n is the integer 1 or 2; Z is loweralkyl; and m is an integer from 0 to
 4. 2. The compound of claim 1,N-allyl-N-(1,3-dioxepan-2-ylmethyl)-α-chloroacetamide.
 3. A method ofcontrolling weeds which comprise contacting said weeds with an effectiveamount of a herbicidal composition comprising an inert carrier and, asan essential active ingredient, in a quantity toxic to weeds, a compoundof claim
 1. 4. A compound of the formula ##STR12## wherein R¹ isselected from the group consisting of hydrogen and lower alkyl; X ischlorine or bromine; R² is lower alkynyl; n is the integer 1 or 2; Z islower alkyl; and m is an integer from 0 to
 4. 5. The compound of claim4, N-propargyl-N-(1,3-dioxepan-2-ylmethyl)-α-chloroacetamide.
 6. Amethod of controlling weeds which comprises contacting said weeds withan effective amount of a herbicidal composition comprising an inertcarrier and, as an essential active ingredient, in a quantity toxic toweeds, a compound of claim 4.